Preparation of dyestuffs and pigments



United States Patent Ofilice Patented Feb. 26, 1963.

3,079,376 PREPARATION OF DYESTUFFS AND PIGMENTS HermannA. Bergstrom, Loudonville, Albany, N.Y., as-

signor to General Aniline & Film Corporation, New York, N.'Y., a corporation of Delaware" N Drawing; Filed Feb. 15, 1957, Ser; No. 640,328 10 Claims. (Cl; 260192)- This invention relates to improved anthraquinone v'azoic pigments, and a process of preparing the same.

Whilemany anthraquinone azoic pigments are known in the art, having been disclosed, for example, in US.

Patent No. 1,924,774, but including. pigments made bycoupling a diazotized amino anthraquinone with a 3-hydroxy-Z-naphtharylide (Napthol-AS type coupler), I have.

wherein R R X, Z and Z are asdefined below. i

The novel pigments of the present invention may, therefore, berepresented'bythe following general formula:

I Y O IXN/ wherein Y represents Hand.Cl; R and R each represent H,C alkyl, aryl, or cycloalkyl; and R and R jointly may represent-a mononuclear heterocycle; Z and Z may represent H, and non-solubili zing-substituents such as Br, Cl, N0 lower alkyl, alkoxy, substituted amino in which the substituents are the same asR and R acylarnido, alkyl and aryl sulfonamido and the like; Xrepresents CO 01 S02.

The usual method of preparing anthraquinone-azoic pigments is by-diazotizationof the amino anthraquinone followed by coupling of the thus obtained diazo with the naphthol AS component to immediately form a pigment. I have found, howeven'that with thez-anthraquinone-azoic pigments of the present inventionsatisfactory products are not obtained bythis conventional method since, when so produced, theyare. dull in shade and are sensitive'to alkalies, thus indicating incomplete coupling and a high degree: ofirnpurity. I have found, however, that the anthraquinone-azoic pigments of the present invention may be produced in good yield and with good properties if the amino anthraquinone is reduced to the leuco sulfuric acid ester;and..the diazo of this leuco sulfuric acid ester then formed by conventional: diazotization procedures and then coupled with a 3-hydroxy-2-naphtharylide of the type mentioned above. This coupling is effected in known manners and preferably in an alkaline solution, pH 75-11. The temperature should be maintained in the range of 0 C. to 5 C. since the diazotized leuco sulfuric acid ester of the amino anthraquinone decom- CONH poses readily evenatroom temperature. The leucosulfuric acid estersalreadyhave the advantage of being comparatively soluble so that complete coupling is readily obtained. The leuco sulfuricacid esters of the anthra quinone-azoic pigments obtained in this manner maybe used directly without isolation but in order. to obtain higher purity it is preferred to isolate it as by salting out and redissolving in water, about a l to 30% solution being preferred. The leuco sulfuric acid estersof the anthraquinone-azoic pigments are then oxidized-by the addition of an oxidizing agent-to the solution of the same. and thus converted to the anthraquinone-azoic pigments. The oxidizing agents which may be employed for oxidation of the leuco sulfuric acid esters may be of .the usual oxidizing agents such ashydrogen peroxide, per acids (e.g. persulfuric acid) per sulfates (e.g. sodium persulfate), potassium permanganate, sodium dichromate, ferric chloride and the like. Sodium nitrite is particularly preferred as an oxidizing agent since it isinexpensive, easy to useand leaves no undesirable metalli-c by-products. The oxidizing agent is used in a calculated equivalent amount ofoxidizing agent per leuco tobe oxidized, up to'about-150% excess; After the addition of the oxidize ing agent it is advantageous to warm'thereacti on mixture for a while, for examplefr'om to 5 hoursata: temperature range from 60 C. to C. On completion of the oxidation the pigment is filtered, washed and dried in "any suitablemanner, or, if desired, the pigment'can be recovered and used-as a paste. In carrying out the oxidation it has been found preferable and advantageous to effect the oxidation in the presence of. a smallamount of polymeric-N-vinyl-u-pyrroli-done in the-manner described in my copendingv application Serial No. 616,135, filed October-16, 1956'.

The amino anthraquinoneswhich I'have found to. be useful in producing the novel products of the present-hi1 vention include: l aminoanthraquinone Z-aminoanthraquinone 1-amino-2-chloroanthraquinone 1 amino-4-chloroanthraquinone 1=amino-5-ch1oroanthraquinone 1-amino-fi-chloroanthraquinone' Z-amino-l-chloroanthraquinone 2-amino-3chloroanthraquinone Of these the chloro substituted amino anthraquinones are particularly preferred since it has been. found that the pigments produced from them have greater light fastness.

The 3-hydroxy-2-naphtharylides of'th'e type indicated above which are useful ascoupling components in preparation of the novelpigrnents of the present invention include those obtainedby, condensing the acid chloride of '3 hydroxy-2 naph'thoic acid with the followingarninesi 3.-aminobenzamide 3-aminobenzanilide I 4-aminobenzamide 4-amino-N-methylbenzamide 4-amino-N,N-dimethylbenzamide 4-amino-N,N-diethylbenzamide 4-amino-Nisopropylbenzamide 4-amino-N-butylbenzamide 4-amino-N-cycloh'exylbenzamide l -amino-N,N dicyclohexylbenzamide 4-amino-N-phenylbenzamide 4-aminobenzomorpholide 4-aminobenzopiperidide 4-amino-2-chlo-ro-N,N-dimethylbenzamide 4-amino-3-ch1oro-N-butylbenzami de 4-amino-3,S-dichlorobenzarriide 4-amino-3,S-dibrornobenzanilide 4-amino-2-nitrobenzanilide The detailed preparation of the products of the present invention and preferred products are illustrated by the following specific examples in which the parts are by weight and from which details of the present invention will be apparent to those skilled in the art.

- The following examples illustrate the invention:

Example 1 42.9 parts of the sodium salt of l-aminoanthraquinone- 9,16-dihydrodisulfuric acid ester are dissolved in 200 parts water and iced to 0 C. 29 parts hydrochloric acid 20 B. are now added. The resulting hydrochloride is diazotized by the slow addition of 6.9 parts sodium nitrite as a 31.5% solution. The temperature is maintained below 5 C. by addition of ice. The diazo slurry is run into a solution (at O-5 C.) of 36.2 parts of on ooNHOooNnoim dissolved in 180 parts water and 10 parts caustic soda (30% by wt. soln.), always keeping the coupling alkaline by further addition of caustic soda solution as needed (pH 7.5-9.5). The alkaline solution is agitated for 1 hr. and then salted with sodium chloride in order to precipitate the dyestufi, which is then filtered.

This soluble dyestufi is converted to the pigment by hydrolysis and oxidation as follows: The dye is dis- 'solved in 1500 parts water and heated to 7080 C. 13 parts sodium nitrite (31.5% soln.) are added. Under rapid agitation, 95 parts hydrochloric acid 20 B. are added. Foaming may occur. The slurry is heated to and maintained at 7090 C. for /21 hr. The pigment is isolated by filtering and washing acid free. A red pigment is obtained by the formula:

Example 2 429 parts of the sodium salt of Z-aminoanthraquinone- 9,10-dihydrodisulfuric acid ester is diazotized as in Example 1. The diazo slurry is run into a solution (0-5 C.) of 33.4 parts of the naphthol:

o QNH-O-CONKJIL);

dissolved in 200 parts water and 10 parts caustic soda (30% by wt. soln.), always keeping the coupling alkaline (pH 7.5-9.5) by addition of more caustic soda. The solution is salted with sodium chloride and the dyestuit filtered. On hydrolysis and oxidation, as in Example 1, a red pigment is produced of the formula:

n I (EONH-OONUJHQ: with;

Example 3 The diazonium chloride from 46.3 parts 2-amino-3- chloroanthraquiuone-9,lO-dihydrodisulfuric acid ester sodium salt is prepared as in Example 1. The diazo slurry is run into 34.8 parts (0-5 C.) of:

dissolved in 200 parts water and 10 parts caustic soda (30% by Wt. soln.) maintaining the coupling alkaline (pH 7.5-9.5) by the addition of caustic as needed. The solution is salted with sodium chloride. After stirring for 1 hr. or longer, the dye is filtered. On hydrolysis and oxidation, as in Example 1, a bright red pigment is produced which has very good light fastness. Its formula is:

o no OONHO ll Example 4 CONE OH (CH The diazonium chloride is prepared from 46.3 parts 2-amino-3-chloroanthraquinone 9,10 dihydrodisulturic acid ester disodium salt as in Example 1. The diazo slurry is run into (at 0-5 C.) a solution of 38.2 parts of the coupling component of the formula:

has the formula:

i HO

CONH

Example The: diazoniurn chloride" from 46.3 parts 1-amino-2- chloroanthraquinone-9,IO-dihydrodisulfuric acid ester so? dium salt is prepared as in Example 1. The diazo is runinto a solution (0-5 Q). 01542.4 parts of acompound. of the formula:

om om V ooNnO-som on (E OHir-QH:

8 dissolvedin 400 parts 30% alcohol solution and parts caustic soda- (30% by. wt. soln.), the coupling being maintained atpI-I 75 9.5 by further addition of caustic. The dye is salted out andfiltered.v Qn hydrolysis and oxidation as in Example-1 an orange pigmentis obtained of Example 6 The diazonium from 463 parts 2,-amino-1-chloroanthaquinone19,IO-dihydrodisulfuric acid ester sodium: salt; prepared as in Example 1, is run into a; solution (0-5 C.) of 42.6 parts of the compound:

CHz-CH:

SQ2N

70H; I \O CHr-Cr CH3 dissolved-in 120 parts alcohol, 10 partscaustic soda (30% by vol. soln.) andflZOO'parts water, always keeping the coupling alkaline. The dye is salted out and filtered. On hydrolysis and oxidation as in Example 1 a red pigment is obtained of the formula:

CHr-CH: SOzN 0.

CH-Cf H? C ONH- Example 7 The diazonium of Example 4 is-run into a solution (0-5 C.) of 37.4 parts of the compound ofthe formula:

OONHOGON\ on,

CHe-Cz dissolved in 120 parts ethyl alcohol, 10 parts caustic soda 30% by vol. soln.) and200 parts Water, always maintaining an alkalinity of pH 7.59t5 byaddition or: more caustic. The dye isisolated by salting out and-filtering.- On hydrolysis and oxidation a red' pigment is obtained of the formula:

CHr-CH: 0 H? CIlONH OON\ /CH1 om-om N=N- Example 8 35.5 parts of the 'leuco dye of the formula:

0S OaNa osoaNa prepared as in Example 2; is\ dissolved in 1000 parts water. The solution is warmed to 75 C. 22.5" parts ferric chloride as a solution and 52 parts hydro- CHr-CH:

chloric acid 20 Be. are combined and addedito the leuco solution. After heating for 1 /2 hrs. ati80 -85 C., filtering, washing and drying, a-redpigment isaobtainedi Example 9" Following the procedure used in Example 1, 46.3 parts 1 amino 6 chloroanthraquinone 9,10 dihydrodisulfuric acid ester sodium salt are diazotized and coupled with 38.8 parts of the BQN ofv 4-aminoi-N-cyolohexylbenzamidea and-lhydr olyzed and: oxidized to; give: a1 pigment of the formula:

0 ONHG-CONHCuH Example 10 Following-the procedure used in Example 1, 46.3 parts 2 amino 3 chloroanthraquinone 9,10 dihydrodisulfuric acid ester-"sodium salt are diazotized and coupled with 40.4 parts of the BON of- 4-amino-3-ehloro-N,N- dimethylbenzenesulfonarnide, and hydrolyzed and oxidized to give a pigment of the formula:

Example Y 11 I Following'th'e procedure used in Example 1; 4623113118 2 amino 3 chloroauthraquinone 9,10 dihydrodisulfuric acid ester sodium salt are diazotized and coupled with 36.4 parts of the BON of 3-an1ino-4-methoxy-N,N- dimethylbenzamide, and hydrolyzed and oxidized to give a pigment of the formula:

Following the procedure used in Example 1, 46.3 parts 2 amino 3 chloroanthraquinone 9,10 dihydrodisulfuric acid ester sodium salt are diazotized and coupled with 35.1 parts of the BON of 4-amino-2-nitrobenzanilide, and hydrolyzed and oxidized to give a pigment of the formula:

o no CONH-QOQNH: we or Example 13 Example 2 was repeated except that 46.3 parts Z-amino- 3-chloroanthraquinone-9,IO-dihydrodisulfuric acid ester sodium salt is used to form the diazo. The pigment has the formula:

o H CONHOOONGJHQ;

I ll

Example 14 46.3 parts 2-amino-3-chloroanthraquinone-9,IO-dihydro-disulfuric acid ester sodium salt is diazotized and coupled with 34.8 parts of:

and the solution salted and filtered as in Example 3.

I claim:

1. Insoluble pigments of the anthraquinone-azoic series which have the formula:

o ll Z2 r N=N Z1 7 ll wherein Y represents a member of the group consisting of hydrogen and chlorine, R and R each represents a member of the group consisting of H, and lower alkyl of l to 4 carbons, phenyl and cycloalkyl radicals and R and R jointly may represent a mononuclear heterocyclic residue; Z and Z each represent a member of the group consisting of H, chlorine, bromine, nitro, lower alkyl, lower alkoxy, methyl amino and dimethyl amino;

8 and X represents a member of the group consisting of -CO- and -S0 groups.

2. Insoluble pigments of the anthraquinone-azoic series which have the formula:

/H CON 1 no CONH lower alkyl z: N=N- Z wherein Y represents a member of the group consisting of hydrogen and chlorine; and Z and Z each represent a member of the group consisting of hydrogen chlorine, bromine, nitro, lower alkyl, lower alkoxy, methyl amino and dimethyl amino.

3. Insoluble pigments of the anthraquinone-azoic series which have the formula:

O 0 N\ O 0 C ONH- lower alky II Z2 -N:N 1 m wherein Z and Z each represent a member of the group consisting of hydrogen, chlorine, bromine, nitro, lower alkyl, lower alkoxy, methyl amino and dimethyl amino.

4. Insoluble pigments of the anthraquinone-azoic series which have the formula:

0 HO GONHO ll 5. Insoluble pigments of the anthraquinone-azoic series 6. Insoluble pigments of the anthraquinone-azoic series which have the formula:

C ONECH(CH3);

lower alkyl C O N lower alkyl CON H O C O NH lower alkyl 1 z: N=N Z I 0 wherein Z and Z each represent a member of the group 9 10 consisting of hydrogen, chlorine, bromine, nitro, lower 10. Insoluble pigments of the anthraquinone-azoic series alkyl, lower alkoxy, methyl amino and dimethyl amino. which have the formula:

7. Insoluble pigments of the anthraquinone-azoic series which have the formula:

5 XN (I) no coring-cement), N no CONE E N N=N zl GI 10 01 II I o o 8. Insoluble pigments of the anthraquinone-azoic series which have the formula: wherein R and R each represents a member of the ECONHO wherein Y represents a member of the group consisting group consisting of H, and lower alkyl of l to 4 carbons, of hydrogen and chlorine; and Z and Z each represent phenyl and cycloalkyl radicals and R and R jointly a member of the group consisting of hydrogen, chlorine, may represent a mononuclear heterocyclic residue; Z bromine, nitro, lower alkyl, lower alkoxy, methyl amino and Z each represent a member of the group consisting and dimethyl amino. of H, chlorine, bromine, nitro, lower alkyl, lower alkoxy, 9. Insoluble pigments of the anthraquiuone-azoic series methyl amino and dimethylamino; and X represents a which have the formula: 30 member of the group consisting of CO-- and SO groups. 0 0 Ho CONE References Cited in the file of this patent l I 35 UNITED STATES PATENTS 1,924,774 Fairweather et al Aug. 29, 1933 2,208,363 Fischer July 16, 1940 01 

1. INSOLUBLE PIGMENTS OF THE ANTHRAQUINONE-AZOIC SERIES WHICH HAVE THE FORMULA: 